Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries

Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.

Electric field and force characteristic of dust aerosol particles on the surface of high-voltage transmission line

High-voltage transmission lines play a crucial role in facilitating the utilization of renewable energy in regions prone to desertification. The accumulation of atmospheric particles on the surface of these lines can significantly impact corona discharge and wind-induced conductor displacement. Accurately quantifying the force exerted by particles adhering to conductor surfaces is essential for evaluating fouling conditions and making informed decisions. Therefore, this study investigates the changes in electric field intensity along branched conductors caused by various fouling layers and their resulting influence on the adhesion of dust particles. The findings indicate that as individual particle size increases, the field strength at the top of the particle gradually decreases and eventually stabilizes at approximately 49.22 k V/cm, which corresponds to a field strength approximately 1.96 times higher than that of an unpolluted transmission line. Furthermore,when particle spacing exceeds 15 times the particle size, the field strength around the transmission line gradually decreases and approaches the level observed on non-adhering surface. The electric field remains relatively stable. In a triangular arrangement of three particles, the maximum field strength at the tip of the fouling layer is approximately 1.44 times higher than that of double particles and 1.5 times higher compared to single particles. These results suggest that particles adhering to the transmission line have a greater affinity for adsorbing charged particles. Additionally, relevant numerical calculations demonstrate that in dry environments, the primary adhesion forces between particles and transmission lines follow an order of electrostatic force and van der Waals force. Specifically, at the minimum field strength, these forces are approximately74.73 times and 19.43 times stronger than the gravitational force acting on the particles.

How do high-voltage cathode and PEO electrolyte get along well?EIS analysis mechanism&potentiometric control strategy

PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.

Degradation analysis and doping modification optimization for high-voltage P-type layered cathode in sodium-ion batteries

Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.

Understanding the failure mechanism towards developing high-voltage single-crystal Ni-rich Co-free cathodes

Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.

High-Voltage and Fast-Charging Lithium Cobalt Oxide Cathodes: From Key Challenges and Strategies to Future Perspectives

Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.

–C≡N functionalizing polycarbonate-based solid-state polymer electrolyte compatible to high-voltage cathodes

Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.

Pairing nitroxyl radical and phenazine with electron-withdrawing/-donating substituents in “water-in-ionic liquid” for high-voltage aqueous redox flow batteries

Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,safety and low cost.However,the underexplored redox properties of organic materials and the narrow thermodynamic electrolysis window of water(1.23 V)hinder their wide applications.Therefore,seeking suitable organic redox couples and aqueous electrolytes with a high output voltage is highly suggested for advancing the aqueous organic RFBs.In this work,the functionalized phenazine and nitroxyl radical with electron-donating and electron-withdrawing group exhibit redox potential of-0.88 V and 0.78 V vs.Ag,respectively,in“water-in-ionic liquid”supporting electrolytes.Raman spectra reveal that the activity of water is largely suppressed in“water-in-ionic liquid”due to the enhanced hydrogen bond interactions between ionic liquid and water,enabling an electrochemical stability window above 3 V.“Water-in-ionic liquid”supporting electrolytes help to shift redox potential of nitroxyl radical and enable the redox activity of functionalized phenazine.The assembled aqueous RFB allows a theoretical cell voltage of 1.66 V and shows a practical discharge voltage of 1.5 V in the“water-in-ionic liquid”electrolytes.Meanwhile,capacity retention of 99.91%per cycle is achieved over 500 charge/discharge cycles.A power density of 112 mW cm^(-2) is obtained at a current density of 30 mA cm^(-2).This work highlights the importance of rationally combining supporting electrolytes and organic molecules to achieve high-voltage aqueous RFBs.

计及IGBT结温约束的光伏高渗透配电网无功电压优化控制策略

光伏电源参与配电网无功电压调节是提升光伏高渗透配电网运行经济性和可靠性的有效手段,但光伏电源提供无功支撑会使得光伏电源IGBT最大结温升高、结温波动加剧,进而影响光伏电源和配电网的安全稳定运行。为此,该文提出一种计及IGBT结温约束的光伏高渗透配电网无功电压优化控制策略。首先,利用CatBoost算法计算IGBT结温,提高了IGBT结温计算效率,避免了传统结温算法对IGBT热模型参数的依赖;然后,建立考虑IGBT结温约束的有源配电网多目标无功优化模型,利用二分法求解IGBT结温约束下的光伏电源最大输出功率,实现了IGBT结温约束向二阶锥约束的转换;最后,利用IEEE33节点典型配电系统验证了所提策略在光伏高渗透配电网无功电压优化、光伏电源运行可靠性提升方面的有效性,并提出了综合考虑配电网网损、光伏电源可靠性的光伏电源IGBT结温限值整定原则。

基于注意力机制的CNN-BiLSTM的IGBT剩余使用寿命预测

针对绝缘栅双极型晶体管(IGBT)可靠性问题,提出了一种融合卷积神经网络(CNN)、双向长短期记忆(BiLSTM)网络和注意力机制的剩余使用寿命(RUL)预测模型,可用于IGBT的寿命预测。模型中使用CNN提取特征参数,BiLSTM提取时序信息,注意力机制加权处理特征参数。使用IGBT加速老化数据集对提出的模型进行验证。结果表明,对比自回归差分移动平均(ARIMA)、长短期记忆(LSTM)、多层LSTM(Multi-LSTM)、 BiLSTM预测模型,在均方根误差和决定系数等评价指标方面该模型的性能最优。验证了提出的寿命预测模型对IGBT失效预测是有效的。

用于IGBT模块温度观测的3-D降阶混合型热模型

IGBT模块温度在线监测是提高大容量变流器可靠性的关键技术。在IGBT模块在线温度监测方法中,热阻模型法可对IGBT模块内部的温度分布进行估计,因而受到关注。结合了传感器数据的温度观测器可基于热阻模型,实时修正材料老化、参数温度依赖性和功率损耗计算误差等不确定因素对温度估计造成的影响。然而现有热模型无法同时兼顾系统可观性和建模准确性,且阶数相对较高,难以应用于温度观测器的在线运行。因此,该文提出了一种适用于风冷散热多芯片IGBT模块3-D温度观测器,同时满足可观性、准确性和实时性要求的混合型降阶热模型。首先,分析了热阻模型的拓扑结构及其参数辨识的方法,并探究了模型的状态空间生成规律;然后,基于非线性优化算法对该模型的参数进行修正,以减小因计算流体力学(CFD)仿真模型参数与实际参数不一致所引入的热阻模型与实验物理对象间的误差;随后,使用平衡截断法对热阻模型降阶,相对于现有集总参数热阻模型,进一步提高了实时求解效率;最后,通过仿真和实验验证了所提模型的准确性。

基于Bo-BiLSTM网络的IGBT老化失效预测方法

针对绝缘栅双极型晶体管(IGBT)受热应力冲击后对其进行老化失效预测精度不高的情况,提出一种基于贝叶斯优化(Bo)-双向长短期记忆(BiLSTM)网络的IGBT老化失效预测方法。首先分析IGBT模块老化失效原理,然后基于NASA老化实验数据集建立失效特征数据库,最后利用Matlab软件构造Bo-BiLSTM网络预测失效特征参数数据。选取常用回归预测性能评估指标将长短期记忆(LSTM)网络模型、BiLSTM网络模型与Bo-BiLSTM网络模型的预测结果进行对比分析。结果表明,Bo-BiLSTM网络的模型拟合精度更高,基于Bo-BiLSTM网络的IGBT老化失效预测方法具有较好的预测效果,能够应用于IGBT的失效预测。

增强牵引变流器过载的IGBT泵升驱动技术

轨道交通牵引变流器在车辆启动加速和紧急制动过程中,会运行在过载工况,即流过IGBT的电流超过设计的额定电流。此时虽然仍在器件允许电流范围内,但IGBT损耗会出现较大增幅,导致变流器温升大幅波动。研究一种集成门极电压泵升技术的IGBT驱动电路,在需要短时加大IGBT通流能力时,可以将门极开通电压升高,降低IGBT的导通压降,减小IGBT的损耗和温升波动。分析过载工况下的牵引变流器工作特性,并在此基础上计算IGBT的损耗和温升情况;分析门极开通电压升高对IGBT导通压降的影响,并设计具有门极电压泵升功能的IGBT驱动电路。通过仿真和双脉冲动态开关实验,验证此设计功能的有效性。

并联IGBT占空比的温度特性建模与分析

并联IGBT是解决托卡马克(Tokamak)装置中等离子体垂直位移快速控制电源容量逐渐增大问题的有效途径。而并联IGBT之间的结温平衡是并联系统安全稳定运行的关键因素之一。因此,研究结温对并联IGBT功率损耗差异的影响对提高并联系统的稳定性至关重要。然而现有的研究成果主要集中在单个器件损耗模型或者是并联IGBT的最佳工作频率范围而未涉及对并联IGBT最佳工作占空比范围的讨论。研究发现,当IGBT工作在正温度系数区间时,结温差异造成的通态损耗差异与开关损耗差异呈不同的温度特性。因此,提出零温度-占空比的概念来估计并联IGBT之间结温失配趋势。该文建立零温度-占空比模型,并以此来分析电路设计参数、IGBT器件参数以及结温差异对并联IGBT最佳工作占空比范围的影响。实验结果表明,通过零温度-占空比模型可以对并联IGBT的可靠性、电路设计参数以及器件选型提供可行的参考。

基于改进DBO优化BiLSTM的IGBT老化预测模型

为了表征逆变器故障中IGBT模块的老化趋势,提高老化过程的预测精度,本文提出一种基于改进蜣螂搜索算法(IDBO)优化双向长短期神经网络(BiLSTM)超参数的IGBT老化预测模型。首先提取老化过程中Vce.on的时频域特征,利用核主成分分析进行降维构建归一化综合指标。其次,针对蜣螂搜索算法(DBO)的不足,通过引入改进Circle混沌映射、Levy飞行和自适应权重因子提升了DBO寻优能力和收敛性能,利用IDBO对BiLSTM预测模型超参数实现全局寻优。最后,通过实际IGBT退化数据验证了基于IDBO优化BiLSTM老化预测模型的有效性和优越性。结果表明,所构建的IDBO-BiLSTM模型与BiLSTM模型相比RMSE平均下降36.42%、MAE平均下降31.77%、MAPE平均下降41.03%。

基于干冰微粒喷射冷却的高速列车IGBT散热器设计

针对高速列车IGBT模块的高效散热问题,设计了一种应用于干冰微粒喷射冷却的针肋散热器。建立了3组不同针肋参数模型,通过数值模拟研究分析了针肋数量、直径、高度对散热效果的影响,得出最优针肋散热器的针肋数量为64、直径为12 mm、高度为45 mm,相比于无肋散热器其换热基板表面温度降低了10.57℃,散热器内部干冰升华率提高了17.2%。通过实验观测到了干冰微粒冷却流体在管内流动状态以及干冰微粒在散热器内部扰动碰撞过程,验证了模拟结果,干冰微粒喷射冷却使热源功率为1.6 kW的IGBT模块保持在约25℃,满足其散热需要,为深入研究干冰微粒喷射冷却技术提供指导。

IGBT动态雪崩失效机理仿真分析

IGBT在关断过程中所发生的动态雪崩现象是导致其失效的重要原因之一。为研究IGBT动态雪崩失效机理,利用Silvaco软件对其进行仿真分析。通过对动态雪崩击穿机制、电流密度分布和温度分布的仿真分析,得出动态雪崩可以产生移动的电流丝和移动十分缓慢或固定不动的“死丝”。引起器件失效的是动态雪崩形成的死丝,死丝会导致IGBT内局部温度的急剧增加,最终因局部温度过高烧毁器件导致IGBT的失效。在此基础上分析了死丝产生的原因并进一步提出防止IGBT动态雪崩失效的具体措施。

基于稳态集-射极饱和电压的IGBT功率模块疲劳失效模型的研究

随着绝缘栅双极型晶体管(insulated gate bipolar transistor, IGBT)功率模块在民用和军用领域应用的不断深入,IGBT功率模块在长时间电-热应力下的疲劳老化问题越来越突出。本文基于半导体物理和器件可靠性理论,研究IGBT功率模块封装失效的产生原因,分析焊料层和键丝失效的作用机理和表现特征。在研究IGBT通态电压模型的基础上,提出了一种基于稳态集-射极饱和电压的IGBT功率模块疲劳老化模型,实现对焊料层疲劳和键丝疲劳等封装老化问题的综合表征。搭建IGBT功率模块的电-热老化实验测试平台,进行了功率循环老化实验验证,结果表明本文模型可以较为准确地评估IGBT功率模块封装的疲劳老化程度。

电动汽车IGBT剩余使用寿命预测

引入一种基于贝叶斯优化(BOA)的双向长短时记忆网络(Bi-LSTM),同时结合注意力机制,应用于绝缘栅双极型晶体管(IGBT)剩余使用寿命预测,所提方法可有效提高IGBT剩余使用寿命预测的准确性.通过IGBT加速老化试验收集V CE-on,验证了其作为失效特征参数的可行性,并将其作为实验数据集对所提方法进行仿真验证.实验分析结果表明,所提的混合预测模型与经典LSTM及其他预测模型相比,有更低的退化预测误差,具备较高的理论意义和实践价值.

基于失效演化模拟的电力机车用IGBT模块解析剩余寿命建模研究

牵引变流器作为电力机车系统中最关键且故障率最高的设备,影响系统的安全运行,其中绝缘栅双极晶体管(insulated gate bipolar transistor,IGBT)模块是导致牵引变流器失效的主要部件。开展IGBT模块剩余寿命准确评估,对降低运维成本和系统故障率具有重要的战略价值和经济意义。目前采用“里程修”的运维方式,未考虑机车运行线路、工况、负载差异等因素对寿命的影响,导致一些线路过早更换的高昂运维成本和一些线路过晚替换的系统停运风险。因此,在牵引系统IGBT模块故障率高、运行线路间可靠性差异大且采用不合理的“里程修”方式背景下,目前业界普遍关心的问题是各线路基于固定里程修更换的IGBT模块剩余寿命是多少。该文针对电力机车用IGBT模块剩余寿命准确评估的问题,以IGBT模块焊料层不同服役里程空洞尺寸分布规律为基础,建立考虑焊料层空洞空间分布规律的精细化多物理场模型,开展多芯片并联IGBT模块失效演化物理过程模拟,提出以焊料层空洞分布统计规律为老化状态的电力机车用IGBT模块解析剩余寿命预测模拟,并通过功率循环试验验证改进模型准确性。研究成果丰富功率器件的寿命预测和可靠性评估理论,为系统从“里程修”向“状态修”转变提供科学依据。